CN102876268A - Phenolic aldehyde type cyanate ester adhesive - Google Patents
Phenolic aldehyde type cyanate ester adhesive Download PDFInfo
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- CN102876268A CN102876268A CN2012103870695A CN201210387069A CN102876268A CN 102876268 A CN102876268 A CN 102876268A CN 2012103870695 A CN2012103870695 A CN 2012103870695A CN 201210387069 A CN201210387069 A CN 201210387069A CN 102876268 A CN102876268 A CN 102876268A
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Abstract
The invention discloses a phenolic aldehyde type cyanate ester adhesive, relates to a cyanate ester adhesive, and aims to solve the problem of low toughness of the conventional phenolic aldehyde type cyanate ester adhesive. The phenolic aldehyde type cyanate ester adhesive is prepared from the following components in part by mass: 90 to 100 parts of linear phenolic aldehyde type cyanate ester resin, 1 to 50 parts of bisphenol A cyanate ester resin prepolymer, 1 to 30 parts of toughening agent, 5 to 50 parts of fibrous filler, 0.05 to 3 parts of curing catalyst and 1 to 10 parts of curing accelerator. By the phenolic aldehyde type cyanate ester adhesive, the advantages of the excellent high temperature resistance, burning resistance, and high-temperature mechanical property of phenolic aldehyde type cyanate ester are guaranteed, the toughness is improved simultaneously, and the peel strength is greatly improved and can reach 26.89N/cm at the temperature of 90 DEG C; and the phenolic aldehyde type cyanate ester adhesive is a high temperature-resistant and high-toughness adhesive and can be applied to the fields of aerospace, electronics and the like.
Description
Technical field
The present invention relates to a kind of cyanate tackiness agent.
Background technology
Novolac Cyanate Eater Resin (PT resin) is a class that has unique texture in the cyanate family, it the skeleton of linear phenolic aldehyde introduce cyanate functional group (OCN) obtain:
In the formula: n=2～7
The PT resin has than the better dielectric properties of the mature performance resins such as resol, Resins, epoxy and bimaleimide resin, mechanical property and heat-resisting, ablation resistance etc., can be used as the uses such as electromagnetic wave transparent material, structured material, high temperature resistant adhesives.
After the PT resin solidifies through hot polymerization, form the rock steady structure of the triazine ring that is connected by the phenylate key, this has given resin higher heat-resisting oxygen, ablation resistance and intensity.The glass transition temperature Tg of PT resin cured matter＞350 ℃ are near 450 ℃ of heat decomposition temperatures; When burning, the cured article surface produces coke, protects lower floor's material and then has strengthened flame retardant resistance.Compare with resol, the PT resin has better thermo-oxidative stability and higher carbon residue amount.In fields such as space flight and aviation, the PT resin can replace traditional resol, has application prospect.
Because molecular memory is at a large amount of oxygen-ether linkages, the PT resin is the higher class of toughness in the high-performance thermosetting resin, but consider from the angle of molecular structure, the PT resin is after solidifying fully, cross-linking density is too large, exist a large amount of phenyl ring, the rigid structure of triazine ring in the structure, show as hard brittle material aspect mechanical property, its flexural strength, tensile strength only are 1/2 of bisphenol A cyanate ester.But in many application scenarios, the interlaminar shear strength of its fracture toughness property and matrix material is also not enough.
In sum, the PT resin has resistant to elevated temperatures advantage, but toughness little be its shortcoming, 90 ° of stripping strengths of existing PT resin adhesive only are about 3N/cm, can't have high temperature resistant and two advantages of high tenacity concurrently.Desirable mode is that the PT resin is done toughening modifying, keeping improving toughness on high temperature resistant, the anti-basis of burning performance, prepares thus high temperature resistant, high tenacity adhesive.
Summary of the invention
The present invention will solve the existing little problem of Novolac Cyanate Eater Resin tackiness agent toughness, and a kind of Novolac Cyanate Eater Resin tackiness agent is provided.
A kind of Novolac Cyanate Eater Resin tackiness agent of the present invention is to be made by 90～100 parts of linear Novolac Cyanate Ester Resins, 1～50 part of bisphenol A cyanate ester resin prepolymer, 1～30 part of toughner, 5～50 parts of fibrous packing, 0.05～3 part of curing catalysts and 1～10 part of curing catalyst by mass fraction.
Novolac Cyanate Eater Resin tackiness agent of the present invention adds a small amount of bisphenol A cyanate ester prepolymer again take Novolac Cyanate Eater Resin as matrix resin, forms the reaction resin system of Novolac Cyanate Eater Resin tackiness agent of the present invention; The present invention also adds the polyaryl sulphone with toughner function, effect is to reduce the fragility of cyanate ester resin, significantly improve the toughness of tackiness agent, Novolac Cyanate Eater Resin tackiness agent of the present invention had both guaranteed that Novolac Cyanate Eater Resin high temperature resistantly, anti-burnt, the advantage of mechanical behavior under high temperature excellence, improved simultaneously toughness, stripping strength significantly improves, 90 ° of stripping strengths can reach 26.89N/cm, are a kind of high temperature resistant, high tenacity adhesives.
Embodiment
Embodiment one: a kind of Novolac Cyanate Eater Resin tackiness agent of present embodiment is to be made by 90～100 parts of linear Novolac Cyanate Ester Resins, 1～50 part of bisphenol A cyanate ester resin prepolymer, 1～30 part of toughner, 5～50 parts of fibrous packing, 0.05～3 part of curing catalysts and 1～10 part of curing catalyst by mass fraction.
The Novolac Cyanate Eater Resin tackiness agent of present embodiment adds a small amount of bisphenol A cyanate ester prepolymer again take Novolac Cyanate Eater Resin as matrix resin, forms the reaction resin system of Novolac Cyanate Eater Resin tackiness agent of the present invention; The present invention also adds the polyaryl sulphone with toughner function, effect is to reduce the fragility of cyanate ester resin, significantly improve the toughness of tackiness agent, tackiness agent of the present invention had both guaranteed that Novolac Cyanate Eater Resin high temperature resistantly, anti-burnt, the advantage of mechanical behavior under high temperature excellence, improved simultaneously toughness, stripping strength significantly improves, 90 ° of stripping strengths can reach 26.89N/cm, are a kind of high temperature resistant, high tenacity adhesives.
Embodiment two: what present embodiment and embodiment one were different is that the cyanate tackiness agent is to be made by 100 parts of linear Novolac Cyanate Ester Resins, 25 parts of bisphenol A cyanate ester resin prepolymers, 10 parts of toughner, 10 parts of fibrous packing, 1 part of curing catalysts and 5 parts of curing catalysts by mass fraction.Other is identical with embodiment one.
Embodiment three: what present embodiment was different from embodiment one or two is that the general formula of linear phenolic aldehyde cyanate ester resin is:
In the formula: n=2～7.Other is identical with embodiment one or two.
Embodiment four: what present embodiment was different from one of embodiment one to three is that toughner is polyarylsulphone.Other is identical with one of embodiment one to three.
Embodiment five: what present embodiment was different from one of embodiment one to four is that fibrous packing is the mixture that glass fibre, carbon fiber or glass fibre and carbon fiber are mixed by any ratio.Other is identical with one of embodiment one to four.
Embodiment six: what present embodiment was different from one of embodiment one to five is that curing catalysts is acetylacetone copper.Other is identical with one of embodiment one to five.
Embodiment seven: what present embodiment was different from one of embodiment one to six is that curing catalyst is nonyl phenol.Other is identical with one of embodiment one to six.
By following verification experimental verification beneficial effect of the present invention:
Test 1
Test is divided into test group and control group.
1, the preparation of bisphenol A cyanate ester resin prepolymer
500g bisphenol A cyanate ester monomer is warmed up to more than 80 ℃, until be dissolved as the homogeneous colourless liquid fully, continue slowly to be warmed up to 150 ℃, then under agitation add the 15g catalyzer, keep temperature of reaction in 150～155 ℃ of intervals, about coreaction 1h, between the reaction period, take out a small amount of product with glass stick, observe the viscosity flow state after the cooling, along with reaction is carried out, the monomer crystallisate reduces gradually, until without obviously crystallisate appearance, the bisphenol A cyanate ester resin prepolymer that obtain this moment is the faint yellow high thick liquid of homogeneous, wherein catalyzer is acetylacetone copper.
2, the preparation of Novolac Cyanate Eater Resin tackiness agent
Test group 1 Novolac Cyanate Eater Resin tackiness agent is to be made by 100 parts of linear Novolac Cyanate Ester Resins, 30 parts of bisphenol A cyanate ester resin prepolymers, 2 parts of terminal hydroxy group polyarylsulphone, 15 parts of glass fiber powders, 1 part of acetylacetone copper and 4.5 parts of nonyl phenols by mass fraction.Its preparation method is: the bisphenol A cyanate ester resin prepolymer that at first 100 parts of linear Novolac Cyanate Ester Resins and 30 parts of these tests is made mixes, add respectively again 2 parts of terminal hydroxy group polyarylsulphone, 15 parts of glass fiber powders, 1 part of acetylacetone copper and 4.5 parts of nonyl phenols, namely get test group 1 Novolac Cyanate Eater Resin tackiness agent.
Test group 2 Novolac Cyanate Eater Resin tackiness agent are to be made by 100 parts of linear Novolac Cyanate Ester Resins, 30 parts of bisphenol A cyanate ester resin prepolymers, 5 parts of terminal hydroxy group polyarylsulphone, 12 parts of glass fiber powders, 1 part of acetylacetone copper and 5 parts of nonyl phenols by mass fraction.Its preparation method is: the bisphenol A cyanate ester resin prepolymer that at first 100 parts of linear Novolac Cyanate Ester Resins and 30 parts of these tests is made mixes, add respectively again 5 parts of terminal hydroxy group polyarylsulphone, 12 parts of glass fiber powders, 1 part of acetylacetone copper and 5 parts of nonyl phenols, namely get test group 2 Novolac Cyanate Eater Resin tackiness agent.
Test group 3 Novolac Cyanate Eater Resin tackiness agent are to be made by 100 parts of linear Novolac Cyanate Ester Resins, 25 parts of bisphenol A cyanate ester resin prepolymers, 10 parts of terminal hydroxy group polyarylsulphone, 10 parts of glass fiber powders, 1 part of acetylacetone copper and 4.5 parts of nonyl phenols by mass fraction.Its preparation method is: the bisphenol A cyanate ester resin prepolymer that at first 100 parts of linear Novolac Cyanate Ester Resins and 25 parts of these tests is made mixes, add respectively again 10 parts of terminal hydroxy group polyarylsulphone, 10 parts of glass fiber powders, 1 part of acetylacetone copper and 4.5 parts of nonyl phenols, namely get test group 3 Novolac Cyanate Eater Resin tackiness agent.
Test group 4 Novolac Cyanate Eater Resin tackiness agent are to be made by 100 parts of linear Novolac Cyanate Ester Resins, 30 parts of bisphenol A cyanate ester resin prepolymers, 15 parts of terminal hydroxy group polyarylsulphone, 10 parts of glass fiber powders, 1 part of acetylacetone copper and 5 parts of nonyl phenols by mass fraction.Its preparation method is: the bisphenol A cyanate ester resin prepolymer that at first 100 parts of linear Novolac Cyanate Ester Resins and 30 parts of these tests is made mixes, add respectively again 15 parts of terminal hydroxy group polyarylsulphone, 10 parts of glass fiber powders, 1 part of acetylacetone copper and 5 parts of nonyl phenols, namely get test group 4 Novolac Cyanate Eater Resin tackiness agent.
Control group 1 Novolac Cyanate Eater Resin tackiness agent is to be mixed by 100 parts of linear Novolac Cyanate Ester Resins, 10 parts of glass fiber powders, 1 part of acetylacetone copper and 5 parts of nonyl phenols by mass fraction.
Control group 2 Novolac Cyanate Eater Resin tackiness agent are to be made by 100 parts of linear Novolac Cyanate Ester Resins, 30 parts of bisphenol A cyanate ester resin prepolymers, 15 parts of glass fiber powders, 1 part of acetylacetone copper and 5 parts of nonyl phenols by mass fraction.Its preparation method is: the bisphenol A cyanate ester resin prepolymer that at first 100 parts of linear Novolac Cyanate Ester Resins and 30 parts of these tests is made mixes, add respectively again 15 parts of glass fiber powders, 1 part of acetylacetone copper and 5 parts of nonyl phenols, namely get control group 2 Novolac Cyanate Eater Resin tackiness agent.
3, testing method
The mechanical property of the Novolac Cyanate Eater Resin tackiness agent that this test obtains is by shearing resistance and stripping strength evaluation, and thermal property is estimated by the thermal weight loss carbon yield.
The shearing resistance testing standard is GB7214-86 tensile shear strength test method; The LY-12CZ aluminium alloy is selected in the strength test test piece.The peel strength test standard is GJB446-1988 tackiness agent 90 degree peeling strength test methods.
The thermal weight loss carbon yield is analyzed: get Novolac Cyanate Eater Resin tackiness agent that 5-10mg solidified with DIAMOND-6300 type thermal weight loss/differential thermal coupling thermal analyzer test carbon yield.Air atmosphere, 10 ℃/min of temperature rise rate, temperature range 20-800 ℃.4, test-results
The shearing resistance of the Novolac Cyanate Eater Resin tackiness agent that this test obtains and the test result of stripping strength see Table 1.
The test result of table 1 shearing resistance and stripping strength
The thermal weight loss carbon yield analytical results of the Novolac Cyanate Eater Resin tackiness agent that this test obtains sees Table 2:
Table 2 is the carbon yield of Novolac Cyanate Eater Resin tackiness agent at each temperature
Can be found out that by table 1 and table 2 the Novolac Cyanate Eater Resin tackiness agent of test group has improved the toughness of PT resin, show as normal temperature shearing, 200 ℃ of shearing resistances and 90 ° of stripping strengths and greatly improve; Guaranteed simultaneously the resistance to elevated temperatures of PT resin, shearing resistance is substantially constant, the high temperature carbon yield is basic identical to show high temperature (300 ℃).
Claims (7)
1. a Novolac Cyanate Eater Resin tackiness agent is characterized in that the cyanate tackiness agent is to be made by 90～100 parts of linear Novolac Cyanate Ester Resins, 1～50 part of bisphenol A cyanate ester resin prepolymer, 1～30 part of toughner, 5～50 parts of fibrous packing, 0.05～3 part of curing catalysts and 1～10 part of curing catalyst by mass fraction.
2. according to claims 1 described a kind of Novolac Cyanate Eater Resin tackiness agent, it is characterized in that the cyanate tackiness agent is to be made by 100 parts of linear Novolac Cyanate Ester Resins, 25 parts of bisphenol A cyanate ester resin prepolymers, 10 parts of toughner, 10 parts of fibrous packing, 1 part of curing catalysts and 5 parts of curing catalysts by mass fraction.
3. according to claims 1 described a kind of Novolac Cyanate Eater Resin tackiness agent, it is characterized in that the general formula of linear phenolic aldehyde cyanate ester resin is:
In the formula: n=2～7.
4. according to claims 1 described a kind of Novolac Cyanate Eater Resin tackiness agent, it is characterized in that toughner is polyarylsulphone.
5. according to claims 1 described a kind of Novolac Cyanate Eater Resin tackiness agent, it is characterized in that fibrous packing is the mixture that glass fibre, carbon fiber or glass fibre and carbon fiber are mixed by any ratio.
6. according to claims 1 described a kind of Novolac Cyanate Eater Resin tackiness agent, it is characterized in that curing catalysts is acetylacetone copper.
7. according to claims 1 described a kind of Novolac Cyanate Eater Resin tackiness agent, it is characterized in that curing catalyst is nonyl phenol.
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| CN2012103870695A CN102876268A (en) | 2012-10-12 | 2012-10-12 | Phenolic aldehyde type cyanate ester adhesive |
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| CN2012103870695A CN102876268A (en) | 2012-10-12 | 2012-10-12 | Phenolic aldehyde type cyanate ester adhesive |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104804185A (en) * | 2015-04-24 | 2015-07-29 | 黑龙江省科学院石油化学研究院 | Cyanate ester prepolymer used for preparing glue film and preparation method of cyanate ester prepolymer |
| CN106189225A (en) * | 2016-08-22 | 2016-12-07 | 威海光威复合材料股份有限公司 | Nano-ceramic powder modified cyanic acid ester resin prepares the method for composite |
| CN112457797A (en) * | 2020-10-27 | 2021-03-09 | 华东理工大学 | High-temperature-resistant cyanate ester conductive adhesive and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104804185A (en) * | 2015-04-24 | 2015-07-29 | 黑龙江省科学院石油化学研究院 | Cyanate ester prepolymer used for preparing glue film and preparation method of cyanate ester prepolymer |
| CN106189225A (en) * | 2016-08-22 | 2016-12-07 | 威海光威复合材料股份有限公司 | Nano-ceramic powder modified cyanic acid ester resin prepares the method for composite |
| CN112457797A (en) * | 2020-10-27 | 2021-03-09 | 华东理工大学 | High-temperature-resistant cyanate ester conductive adhesive and preparation method thereof |
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